WO2014038457A1

WO2014038457A1 - Infrared blocking film

Info

Publication number: WO2014038457A1
Application number: PCT/JP2013/073096
Authority: WO
Inventors: 大関　勝久; 清都　尚治; 亮松野; 峻也加藤
Original assignee: 富士フイルム株式会社
Priority date: 2012-09-05
Filing date: 2013-08-29
Publication date: 2014-03-13
Also published as: JP6076699B2; JP2014066987A

Abstract

This infrared blocking film, which has a metal particle-containing layer having metal particles contained therein, and which contains a compound having absorbing characteristics in an infrared region, is capable of easily reflecting infrared, and has high heat ray reflectivity.

Description

Infrared shielding film

The present invention relates to an infrared shielding film.

In recent years, heat ray shielding materials for automobiles and building windows have been developed as an energy-saving measure for reducing carbon dioxide. From the viewpoint of the heat ray shielding property (acquisition rate of solar heat), the heat ray reflection type without re-radiation is better than the heat ray absorption type with re-radiation of absorbed light into the room (about 1/3 of the absorbed solar energy). Various proposals have been made.

Patent Document 1 discloses a heat ray shielding material having a metal particle-containing layer containing at least one kind of metal particles and a cholesteric liquid crystal layer, wherein the metal particles are substantially hexagonal or disk-shaped metal tabular particles. And a selective reflection wavelength of the cholesteric liquid crystal layer is in the infrared region, and is excellent in visible light transmission and radio wave transmission, and has a short wavelength side infrared ray. It is described that it is possible to provide a heat ray shielding material that has a high shielding rate, can shield infrared rays in a wide band, has low brittleness, and can be thinned. However, when attempting to obtain a reflection peak using liquid crystal, the layer becomes thick even in a narrow band, and thinning is insufficient. In fact, the example of Patent Document 1 also discloses a layer thickness of 20 μm. Further, in order to form the liquid crystal layer, there is a problem that manufacturing is complicated and cost burden is large, such as smoothing the substrate. Further, Patent Document 1 discloses an example containing metal fine particles and showing a reflection peak in the infrared region, but there was no example of using it together with an infrared absorbing dye.

Patent Document 2 discloses a highly robust near-infrared ray having absorption in the near-infrared region and having no absorption in the 400-700 nm region and excellent invisibility due to a pigment fine particle having a pyrrolopyrrole structure and its coating. Absorbable compounds are described. Patent Document 2 discloses an absorption spectrum of a dye, but reflection by the dye cannot be read and is not described. Further, Patent Document 2 neither disclosed nor suggested that an infrared light absorbing material using an infrared dye is used in combination with metal particles.

Patent Document 3 has a film-like support, and a near-infrared absorbing layer formed on the support using a near-infrared absorbing composition containing an aqueous dispersion of a near-infrared absorbing dye and a polymer. In addition, it is described that a near-infrared absorption filter having improved haze value and particularly durability under high temperature and high humidity can be provided by a near-infrared absorption filter having a haze value of 4% or less. Patent Document 3 did not describe reflection by a dye. Further, Patent Document 3 neither disclosed nor suggested that an infrared light absorbing material using an infrared dye is used in combination with metal particles.

JP 2012-108207 A JP 2009-263614 A JP 2008-181096 A

In the embodiment in which the infrared dye described in these documents is used alone, the heat ray shielding ability is insufficient, and further improvement has been desired.

The problem to be solved by the present invention is to provide an infrared shielding film that can easily reflect infrared light and has high heat ray reflectivity.

As a result of intensive studies to solve the above-mentioned object, the present inventors have found that a reflection band due to a dye is generated near the maximum absorption wavelength (spectral wavelength) by applying a thin layer of the dye (hereinafter referred to as abnormal reflection). Also called). Further, by combining the metal particles and the infrared absorbing dye, infrared light can be reflected more easily than the infrared shielding films described in Patent Documents 1 to 3, and the above problems are caused because the heat ray reflectance is increased. The inventors have found that the problem can be solved and have completed the present invention.

The present invention, which is a specific means for solving the above problems, is as follows.
[1] An infrared shielding film comprising a metal particle-containing layer containing metal particles and a compound having absorption in the infrared region.
[2] In the infrared shielding film according to [1], the metal particles preferably have 60% by number or more of flat metal particles.
[3] In the infrared shielding film according to [1] or [2], it is preferable that at least one layer has a transmission spectrum peak in a region of 800 to 2000 nm.
[4] In the infrared shielding film according to any one of [1] to [3], the compound having absorption in the infrared region is a compound represented by the following general formula (1) or the following general formula ( It is preferable that it is a compound represented by 2).

(In the general formula (1), Z ¹ and Z ² are each independently a non-metallic atom group that forms a 5- or 6-membered nitrogen-containing heterocycle. R ¹ and R ² are each independently a fatty group. L ¹ is a methine chain composed of 3 methines. A and b are each independently 0 or 1.)

(In General Formula (2), R ^1a and R ^1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R ² and R ³ each independently represent a hydrogen atom. Or at least one is an electron-withdrawing group, and R ² and R ³ may combine to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted group Represents a boron or metal atom, and may be a covalent bond or a coordinate bond with at least one group of R ^1a , R ^1b and R ^3. )
[5] In the infrared shielding film according to [4], the compound having absorption in the infrared region is preferably a compound represented by the general formula (2).
[6] In the infrared shielding film according to any one of [1] to [5], in the layer containing a compound having absorption in the infrared region, 20 to 190 mg of the compound having absorption in the infrared region. / M ² is preferably included.
[7] In the infrared shielding film according to any one of [1] to [6], the metal particles preferably include at least silver.
[8] In the infrared shielding film according to any one of [1] to [7], it is preferable that the metal particles have 60% by number or more of hexagonal or circular silver tabular grains.
[9] In the infrared shielding film according to any one of [1] to [8], the metal particles are preferably silver tabular grains having an average grain thickness of 20 nm or less.
[10] In the infrared shielding film according to any one of [1] to [9], the metal particles are silver tabular grains having an aspect ratio (average particle diameter / average particle thickness) of 3 to 100. Is preferred.
[11] The infrared shielding film according to any one of [1] to [10] preferably has a transmission peak between 800 nm and the reflection peak of the metal particle in the transmission spectrum.
[12] The infrared shielding film according to any one of [1] to [11] preferably contains an ultraviolet absorber.
[13] The infrared shielding film according to [12] includes an adhesive layer, and the ultraviolet absorber is contained in the adhesive layer or a layer between the adhesive layer and the metal particle-containing layer. preferable.
[14] The infrared shielding film according to any one of [1] to [13] preferably includes a support.
[15] The infrared shielding film according to [14] preferably includes a dye-containing layer containing a compound having absorption in the infrared region on the same side of the support as the metal particle-containing layer.
[16] The infrared shielding film according to [14] or [15] preferably has an undercoat layer between the support and the metal particle-containing layer.
[17] The infrared shielding film according to any one of [14] to [16] preferably has a backcoat layer on the surface of the support opposite to the metal particle-containing layer.
[18] The infrared shielding film according to [17] preferably includes a compound having absorption in the infrared region in at least one of the metal particle-containing layer, the undercoat layer, and the backcoat layer. .

According to the present invention, an infrared shielding film that can easily reflect infrared light and has high heat ray reflectivity can be provided.

FIG. 1 is a schematic view showing an example of the infrared shielding film of the present invention. FIG. 2 is a schematic view showing another example of the infrared shielding film of the present invention. FIG. 3 is a schematic view showing another example of the infrared shielding film of the present invention. FIG. 4 is a schematic view showing another example of the infrared shielding film of the present invention. FIG. 5 is a schematic view showing another example of the infrared shielding film of the present invention. FIG. 6A is a schematic cross-sectional view showing the presence state of a metal particle-containing layer containing metal tabular grains in the infrared shielding film of the present invention, and is a metal particle-containing layer containing metal tabular grains (parallel to the plane of the substrate). ) And the main plane of the metal tabular grain (the plane that determines the equivalent circle diameter D). FIG. 6B is a schematic cross-sectional view showing the existence state of a metal particle-containing layer containing metal tabular grains in the infrared shielding film of the present invention, and the metal tabular grains in the depth direction of the heat ray shielding material of the metal particle-containing layer. FIG. FIG. 6C is a schematic cross-sectional view showing an example of the presence state of a metal particle-containing layer containing metal tabular grains in the infrared shielding film of the present invention. FIG. 6D is a schematic cross-sectional view showing another example of the presence state of a metal particle-containing layer containing tabular metal particles in the infrared shielding film of the present invention. FIG. 6E is a schematic cross-sectional view showing another example of the presence state of a metal particle-containing layer containing metal tabular grains in the infrared shielding film of the present invention. FIG. 7A is a schematic perspective view showing an example of the shape of a metal tabular grain preferably used in the infrared shielding film of the present invention, and shows a circular metal tabular grain. FIG. 7B is a schematic perspective view showing an example of the shape of a metal tabular grain preferably used for the infrared shielding film of the present invention, and shows a hexagonal metal tabular grain. FIG. 8 is a graph showing the reflection spectrum and transmission spectrum of the infrared shielding film and the Blunk film of Example 5 and Comparative Examples 1 and 6.

The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Infrared shielding film]
The infrared shielding film of this invention has the metal particle content layer containing a metal particle, and contains the compound which has absorption in an infrared region.
With such a configuration, infrared light can be easily reflected and an infrared shielding film with high heat ray reflectivity is obtained. Although not bound by any theory, such a configuration can cause abnormal reflection of the dye, increase the reflectance in the infrared region, and improve the heat ray reflectance.
Hereinafter, the more preferable aspect of the infrared shielding film of this invention is demonstrated concretely.

<Characteristics of infrared shielding film>
The infrared ray shielding film of the present invention has an average heat ray reflectance at 700 to 1200 nm of preferably 5% or more, more preferably 7% or more, particularly preferably 8% or more, and 10% or more. More particularly preferred.

In the infrared shielding film of the present invention, it is preferable that at least one layer has the lowest peak of the transmission spectrum in the region of 800 to 2000 nm from the viewpoint of lowering the heat ray transmittance. The minimum peak wavelength of the transmission spectrum is more preferably in the band of 750 to 1400 nm, and particularly preferably in the band of 800 to 1100 nm. In the infrared shielding film of the present invention, the metal particle-containing layer preferably has the lowest peak of the transmission spectrum in the region of 800 to 2000 nm.
The infrared shielding film of the present invention preferably has a transmission peak between 800 nm and the reflection peak of the metal particle in the transmission spectrum from the viewpoint of effectively shielding near infrared rays.

The infrared shielding film of the present invention preferably has a maximum reflection wavelength in a band of 700 to 1800 nm from the viewpoint of increasing the efficiency of heat ray reflection. The maximum reflection wavelength is more preferably in the band of 750 to 1400 nm, and particularly preferably in the band of 800 to 1100 nm.

The visible light transmittance of the infrared shielding film of the present invention is preferably 60% or more, more preferably 65% or more, and particularly preferably 70% or more. When the visible light transmittance is 60% or more, for example, when used as glass for automobiles or glass for buildings, the outside is easy to see.
As an ultraviolet-ray transmittance of the infrared shielding film of this invention, 5% or less is preferable and 2% or less is more preferable.

<Configuration of infrared shielding film>
The infrared shielding film of this invention has a metal particle content layer containing at least 1 type of metal particle, and contains the compound which has absorption in an infrared region. Furthermore, it has other layers such as an undercoat layer, an overcoat layer, an adhesive layer, an ultraviolet absorbing layer, a support (hereinafter also referred to as a base material), a metal oxide particle-containing layer, and a backcoat layer as necessary. Embodiments are also preferred. The layer containing the compound having absorption in the infrared region is not particularly limited, and may be the metal particle-containing layer or any one or more of the other layers.
Hereinafter, the preferable structure of the infrared shielding film of this invention is demonstrated based on drawing.

As shown in FIG. 1, the layer structure of the infrared shielding film 10 includes metal particles containing at least one kind of metal particles on the support 1 through one or more undercoat layers 5. A structure having the layer 2 can be given. The metal particles are preferably metal tabular grains, and an embodiment in which the metal tabular grains 3 are unevenly distributed on the surface of the metal particle-containing layer 2 is preferable. In the configuration of FIG. 1, the compound having absorption in the infrared region is preferably added to at least one of the metal particle-containing layer 2 and the undercoat layer 5.

As shown in FIG. 2, in addition to the structure of FIG. 1, it is preferable to further have a back coat layer 12 on the surface of the support 1 opposite to the metal particle-containing layer 2. In the configuration of FIG. 2, the compound having absorption in the infrared region is preferably added to at least one of the metal particle-containing layer 2, the undercoat layer 5, and the backcoat layer 12.

As shown in FIG. 3, there is an embodiment in which the metal particle-containing layer 2 and the overcoat layer 4 are provided on the metal particle-containing layer 2 and the metal tabular grains 3 are unevenly distributed on the surface thereof. Furthermore, the aspect which has the adhesive layer 11 further on the overcoat layer 4 is mentioned suitably. In the configuration of FIG. 3, the compound having absorption in the infrared region may be added to any layer, but is added to at least one of the metal particle-containing layer 2, the undercoat layer 5, and the backcoat layer 12. Is preferred. In addition, the infrared shielding film 10 preferably includes an ultraviolet absorber in the overcoat layer 4 or the pressure-sensitive adhesive layer 11 in FIG. 3.

As shown in FIG. 4, a metal oxide particle layer 14 including metal oxide particles 13 is provided instead of the backcoat layer 12 on the surface of the support 1 opposite to the metal particle-containing layer 2. Is also preferable. In the configuration of FIG. 4, the compound having absorption in the infrared region may be added to any layer, but is preferably added to at least one of the metal particle-containing layer 2 and an unillustrated undercoat layer.

As shown in FIG. 5, the aspect which has the metal oxide particle layer 14 containing the metal oxide particle 13, the support body 1, the undercoat layer 5, the metal particle content layer 2, the overcoat layer 4, and the adhesive layer 11 is also preferable. . In the configuration of FIG. 5, the compound having absorption in the infrared region may be added to any layer, but is preferably added to at least one of the metal particle-containing layer 2 and the undercoat layer 5.

<Metal particle content layer>
The metal particle-containing layer is a layer containing at least one metal particle.
There is no restriction | limiting in particular in the said metal particle, According to the objective, it can select suitably.
When the thickness of the metal particle-containing layer is d, 80% by number or more of the hexagonal or circular tabular metal particles are present in a range of d / 2 from the surface of the metal particle-containing layer. It is more preferable that it exists in the range of d / 3 from the surface of the said metal-particle content layer. The present invention is not limited to any theory, and the infrared shielding film of the present invention is not limited to the following production method. However, when the metal particle-containing layer is produced, a specific polymer (preferably latex) is used. By adding it, the metal tabular grains can be segregated on one surface of the metal particle-containing layer.

1-1. Metal particles
In the infrared shielding film of the present invention, the metal particles preferably have 60% by number or more of flat metal particles, and more preferably have 60% by number or more of hexagonal or circular plate metal particles.
In the metal particle-containing layer, the form of the hexagonal or circular plate-like metal particles is one surface of the metal particle-containing layer (the surface of the substrate when the infrared shielding film of the present invention has a substrate). On the other hand, the main planes of hexagonal or circular plate-like metal particles are preferably plane-oriented in the range of average 0 ° to ± 30 °, and plane-oriented in the range of average 0 ° to ± 20 °. More preferably, the plane orientation is particularly preferably in the range of 0 ° to ± 10 ° on average.
In addition, it is preferable that one surface of the said metal particle content layer is a flat plane. When the metal particle-containing layer of the infrared ray shielding film of the present invention has a base material as a temporary support, it is preferably substantially horizontal with the surface of the base material. Here, the said infrared shielding film may have the said temporary support body, and does not need to have it.
There is no restriction | limiting in particular as a magnitude | size of the said metal particle, According to the objective, it can select suitably, For example, you may have an average particle diameter of 500 nm or less.
The material of the metal particles is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of high heat ray (near infrared) reflectance, silver, gold, aluminum, copper, rhodium, nickel, Platinum or the like is preferable, and silver is more preferable among them.
The reflection peak of the metal particles is preferably 850 to 1600 nm, and more preferably 900 to 1300 nm. Here, the reflection peak of the metal particles is a reflection peak of the metal particles in the metal particle-containing layer. The reflection peak of the metal particles can be controlled by the material and shape of the metal particles.

-1-2. Tabular grain metal
The metal tabular grain is not particularly limited as long as it is a grain composed of two main planes (see FIGS. 7A and 7B), and can be appropriately selected according to the purpose. For example, hexagonal shape, circular shape, triangular shape Examples include shape. Among these, in terms of high visible light transmittance, a polygonal shape or a circular shape having a hexagonal shape or more is more preferable, and a hexagonal shape or a circular shape is particularly preferable.
In the present specification, the circular shape means 0 per side of a metal tabular grain having a length of 50% or more of the average equivalent circle diameter of a tabular metal grain (synonymous with tabular metal grain) described later. Say the shape that is. The circular tabular metal grains are not particularly limited as long as they have no corners and round shapes when observed from above the main plane with a transmission electron microscope (TEM), depending on the purpose. It can be selected appropriately.
In the present specification, the hexagonal shape means a shape in which the number of sides having a length of 20% or more of the average equivalent circle diameter of the metal tabular grains described later is 6 per one metal tabular grain. The same applies to other polygons. The hexagonal metal tabular grain is not particularly limited as long as it is a hexagonal shape when the metal tabular grain is observed from above the main plane with a transmission electron microscope (TEM), and is appropriately selected according to the purpose. For example, the hexagonal corner may be acute or dull, but the corner is preferably dull in that the absorption in the visible light region can be reduced. There is no restriction | limiting in particular as a grade of the dullness of an angle | corner, According to the objective, it can select suitably.
There is no restriction | limiting in particular as a material of the said metal tabular grain, The same thing as the said metal particle can be suitably selected according to the objective. The metal tabular grain preferably contains at least silver.

Of the metal particles present in the metal particle-containing layer, the hexagonal or circular plate-like metal particles are preferably 60% by number or more, more preferably 65% by number or more based on the total number of metal particles. Preferably, 70% by number or more is particularly preferable. When the ratio of the metal tabular grains is 60% by number or more, the visible light transmittance is increased.

[1-2-1. Planar orientation]
In the infrared shielding film of the present invention, the hexagonal or circular plate-like metal particles have a main plane on one surface of the metal particle-containing layer (when the infrared shielding film has a substrate, the substrate surface). On the other hand, the plane orientation is preferably in the range of average 0 ° to ± 30 °, more preferably the plane is oriented in the range of average 0 ° to ± 20 °, and the average is 0 ° to ± 10 °. It is particularly preferable that the surface is oriented in a range.
The presence state of the metal tabular grains is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably arranged as shown in FIGS. 6D and 6E described later.

Here, FIGS. 6A to 6E are schematic cross-sectional views showing the existence state of the metal particle-containing layer containing the metal tabular grains in the infrared shielding film of the present invention. 6C, FIG. 6D, and FIG. 6E show the presence state of the metal tabular grain 3 in the metal particle-containing layer 2. FIG. 6A is a view for explaining an angle (± θ) formed by the plane of the substrate 1 and the main plane of the metal tabular grain 3 (plane that determines the equivalent circle diameter D). FIG. 6B shows the existence region in the depth direction of the infrared shielding film of the metal particle-containing layer 2.
In FIG. 6A, the angle (± θ) formed by the surface of the substrate 1 and the main plane of the metal tabular grain 3 (the plane that determines the equivalent circle diameter D) or the extension of the main plane is a predetermined value in the plane orientation described above. Corresponds to the range. That is, the plane orientation means a state where the inclination angle (± θ) shown in FIG. 6A is small when the cross section of the infrared shielding film is observed. In particular, FIG. 6D shows the main surface of the substrate 1 and the metal tabular grain 3. A state where the flat surface is in contact, that is, a state where θ is 0 ° is shown. When the angle of the plane orientation of the main plane of the metal tabular grain 3 with respect to the surface of the substrate 1, that is, θ in FIG. 6A exceeds ± 30 °, a predetermined wavelength of the infrared shielding film (for example, near the visible light region long wavelength side) The reflectance in the infrared light region is reduced.

There is no particular limitation on the evaluation of whether or not the main plane of the metal tabular grain is plane-oriented with respect to one surface of the metal particle-containing layer (the surface of the substrate when the infrared shielding film has a substrate). Depending on the purpose, it can be appropriately selected. For example, a suitable cross section is prepared, and the metal particle-containing layer (base material if the infrared shielding film has a base material) and flat metal particles in this section are observed. It may be a method of evaluating. Specifically, a cross-section sample or a cross-section sample of the infrared shielding film is prepared from the infrared shielding film using a microtome and a focused ion beam (FIB), and this is used for various microscopes (for example, a field emission scanning electron microscope ( FE-SEM) etc.), and a method of evaluating from an image obtained by observation.

In the infrared shielding film, when the binder that coats the metal tabular grains swells with water, the sample frozen in liquid nitrogen is cut with a diamond cutter attached to a microtome, so that the cross section sample or cross section sample May be produced. Moreover, when the binder which coat | covers a metal tabular grain in an infrared shielding film does not swell with water, you may produce the said cross-section sample or a cross-section slice sample.

As the observation of the cross-section sample or cross-section sample prepared as described above, the main surface of the metal tabular grains is one surface of the metal particle-containing layer in the sample (the surface of the base material when the infrared shielding film has a base material). There is no particular limitation as long as it can confirm whether or not the plane is plane-oriented, and it can be appropriately selected according to the purpose. For example, observation using an FE-SEM, TEM, optical microscope, or the like can be given. It is done. In the case of the cross section sample, observation may be performed by FE-SEM, and in the case of the cross section sample, observation may be performed by TEM. When evaluating by FE-SEM, it is preferable to have a spatial resolution with which the shape and tilt angle (± θ in FIG. 6A) of the metal tabular grains can be clearly determined.

[1-2-2. Coefficient of variation in particle size distribution of average particle diameter (average equivalent circle diameter)]
In the infrared shielding film of the present invention, the coefficient of variation in the particle size distribution of the metal tabular grains is preferably 35% or less, more preferably 30% or less, and particularly preferably 20% or less. The variation coefficient is preferably 35% or less because the reflection wavelength region of heat rays in the infrared shielding film becomes sharp.
Here, the coefficient of variation in the particle size distribution of the metal tabular grains is, for example, plotting the distribution range of the particle diameters of the 200 metal tabular grains used for calculating the average value obtained as described above, and calculating the standard deviation of the particle size distribution. It is the value (%) obtained by dividing the average value (average particle diameter (average equivalent circle diameter)) of the main plane diameter (maximum length) obtained as described above.

[1-2-3. Metal tabular grain thickness / aspect ratio]
In the infrared shielding film of the present invention, the thickness of the metal tabular grain is preferably 14 nm or less, more preferably 5 to 14 nm, and particularly preferably 5 to 12 nm.
The aspect ratio of the metal tabular grain is not particularly limited and may be appropriately selected depending on the intended purpose. However, since the reflectance in the infrared region with a wavelength of 800 nm to 1,800 nm is high, 40 is preferable, and 10 to 35 is more preferable. When the aspect ratio is less than 6, the reflection wavelength becomes smaller than 800 nm, and when it exceeds 40, the reflection wavelength becomes longer than 1,800 nm, and sufficient heat ray reflectivity may not be obtained.
The aspect ratio means a value obtained by dividing the average particle diameter (average circle equivalent diameter) of the tabular metal grains by the average grain thickness of the tabular metal grains. The average grain thickness corresponds to the distance between the main planes of the metal tabular grain, and is, for example, as shown in FIGS. 7A and 7B and can be measured by an atomic force microscope (AFM).
The method for measuring the average particle thickness by the AFM is not particularly limited and can be appropriately selected depending on the purpose.For example, a particle dispersion containing metal tabular particles is dropped onto a glass substrate and dried. For example, a method of measuring the thickness of one particle may be used.

[1-2-4. Range of tabular metal grains]
In the infrared shielding film of the present invention, the thickness of the region where the metal tabular grains are present is preferably 5 to 60 nm, more preferably 11 to 60 nm, and particularly preferably 20 to 60 nm.
In the infrared shielding film of the present invention, it is preferable that 80% by number or more of the hexagonal or circular tabular metal particles are present in a range of d / 2 from the surface of the metal particle-containing layer, More preferably, it exists in the range, and more preferably 60% by number or more of the hexagonal or circular plate-like metal particles are exposed on one surface of the metal particle-containing layer. The presence of the metal tabular grains in the range of d / 2 from the surface of the metal particle-containing layer means that at least a part of the metal tabular grains is included in the range of d / 2 from the surface of the metal particle-containing layer. . That is, the metal tabular grain described in FIG. 6E in which a part of the metal tabular grain protrudes from the surface of the metal particle-containing layer is also in the range of d / 2 from the surface of the metal particle-containing layer. Treat as. FIG. 6E means that only a part of each metal tabular grain in the thickness direction is buried in the metal particle-containing layer, and each metal tabular grain is not stacked on the surface of the metal particle-containing layer. Absent.
Moreover, that the metal tabular grain is exposed on one surface of the metal particle-containing layer means that a part of one surface of the metal tabular grain protrudes from the surface of the metal particle-containing layer. .
Here, the distribution of the tabular metal particles in the metal particle-containing layer can be measured, for example, from an image obtained by SEM observation of a cross-sectional sample of the infrared shielding film.

In the infrared shielding film of the present invention, as shown in FIG. 6B, the plasmon resonance wavelength of the metal constituting the metal tabular grain 3 in the metal particle-containing layer 2 is λ, and the refractive index of the medium in the metal particle-containing layer 2 is n. When doing, it is preferable that the said metal-particle content layer 2 exists in the range of ((lambda) / n) / 4 in the depth direction from the horizontal surface of an infrared rays shielding film. Within this range, the effect of increasing the amplitude of the reflected wave by the phase of the reflected wave at the interface between the upper and lower metal particle-containing layers of the infrared shielding film is sufficiently large, and the visible light transmittance and maximum heat ray are increased. Reflectivity is good.
The plasmon resonance wavelength λ of the metal constituting the metal tabular grain in the metal particle-containing layer is not particularly limited and can be appropriately selected according to the purpose. However, in terms of imparting heat ray reflection performance, 400 nm to 2, The thickness is preferably 500 nm, and more preferably 700 nm to 2,500 nm from the viewpoint of imparting visible light transmittance.

[1-2-5. Medium of metal particle containing layer]
There is no restriction | limiting in particular as a medium in the said metal particle content layer, According to the objective, it can select suitably. In the infrared shielding film of the present invention, the metal particle-containing layer preferably contains a polymer, and more preferably contains a transparent polymer. Examples of the polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin, and cellulose. And polymers such as natural polymers. Among them, in the present invention, the main polymer of the polymer is preferably a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl chloride resin, a (saturated) polyester resin, a polyurethane resin, and preferably the polyester resin and the polyurethane resin. More preferably, 80% by number or more of the metal tabular grains of hexagonal or circular tabular metal particles are present in the range of d / 2 from the surface of the metal particle-containing layer, and are polyester resin and polyurethane resin. Is particularly preferable from the viewpoint of further improving the rubbing resistance of the infrared shielding film of the present invention.
Among the polyester resins, a saturated polyester resin is more particularly preferable from the viewpoint of imparting excellent weather resistance since it does not contain a double bond. Moreover, it is more preferable to have a hydroxyl group or a carboxyl group at the molecular terminal from the viewpoint of obtaining high hardness, durability, and heat resistance by curing with a water-soluble / water-dispersible curing agent or the like.
Commercially available polymers can be preferably used as the polymer, and examples thereof include Plus Coat Z-867, which is a water-soluble polyester resin manufactured by Kyoyo Chemical Industry Co., Ltd.
Moreover, in this specification, the main polymer of the polymer contained in the metal-containing layer refers to a polymer component occupying 50% by mass or more of the polymer contained in the metal-containing layer.
The content of the polyester resin and the polyurethane resin with respect to the metal particles contained in the metal particle-containing layer is preferably 1 to 10000% by mass, more preferably 10 to 1000% by mass, and 20 to 500% by mass. It is particularly preferred that By setting the binder contained in the metal particle-containing layer to be in the above range or more, physical properties such as rubbing resistance can be improved.
The refractive index n of the medium is preferably 1.4 to 1.7.
In the infrared shielding film of the present invention, when the thickness of the hexagonal or circular plate-like metal particles is a, 80% by number or more of the hexagonal or circular plate-like metal particles are a / in the thickness direction. It is preferable that 10 or more is covered with the polymer, a / 10 to 10a in the thickness direction is more preferably covered with the polymer, and a / 8 to 4a is covered with the polymer. Particularly preferred. As described above, the hexagonal or circular plate-like metal particles are buried in the metal particle-containing layer at a certain ratio or more, whereby the rubbing resistance can be further increased. That is, the aspect of FIG. 6D is more preferable than the aspect of FIG. 6E for the infrared shielding film of the present invention.

[1-2-6. Area ratio of metal tabular grains]
Total value of the area of the metal tabular grains relative to the area A of the base material when viewed from above (the total projected area A of the metal particle-containing layer when viewed from the direction perpendicular to the metal particle-containing layer) The area ratio [(B / A) × 100] which is the ratio of B is preferably 15% or more, and more preferably 20% or more. When the area ratio is less than 15%, the maximum reflectance of the heat ray is lowered, and the heat shielding effect may not be sufficiently obtained.
Here, the area ratio can be measured, for example, by image-processing an image obtained by SEM observation of the infrared shielding film substrate from above or an image obtained by AFM (atomic force microscope) observation. .

[1-2-7. Average distance between tabular grains]
The average inter-particle distance between the metal tabular grains adjacent in the horizontal direction in the metal particle-containing layer is preferably 1/10 or more of the average particle diameter of the metal tabular grains in terms of visible light transmittance and maximum heat ray reflectance. .
When the horizontal average inter-grain distance of the metal tabular grains is less than 1/10 of the average grain diameter of the metal tabular grains, the maximum reflectance of the heat rays is lowered. Further, the average interparticle distance in the horizontal direction is preferably non-uniform (random) in terms of visible light transmittance. If it is not random, that is, if it is uniform, absorption of visible light occurs, and the transmittance may decrease.

Here, the average inter-particle distance in the horizontal direction of the metal tabular grains means an average value of inter-particle distances between two adjacent grains. In addition, the average inter-particle distance is random as follows: “When taking a two-dimensional autocorrelation of luminance values when binarizing an SEM image including 100 or more metal tabular grains, other than the origin. It has no significant local maximum.

[1-2-8. Layer structure of metal particle-containing layer]
In the infrared shielding film of the present invention, the metal tabular grains are arranged in the form of a metal particle-containing layer containing metal tabular grains, as shown in FIGS. 6A to 6E.
The metal particle-containing layer may be composed of a single layer as shown in FIGS. 6A to 6E, or may be composed of a plurality of metal particle-containing layers. When comprised with a several metal particle content layer, it becomes possible to provide the shielding performance according to the wavelength range | band which wants to provide heat insulation performance. When the metal particle-containing layer is composed of a plurality of metal particle-containing layers, the infrared shielding film of the present invention has a thickness d of the outermost metal particle-containing layer at least in the outermost metal particle-containing layer. It is preferable that 80% by number or more of the hexagonal or circular tabular metal particles are present in the range of d ′ / 2 from the surface of the outermost metal particle-containing layer.

[1-2-9. Thickness of metal particle containing layer]
In the infrared shielding film of the present invention, the thickness of the metal particle-containing layer is preferably 5 to 80 nm, and more preferably 6 to 20 nm. The thickness d of the metal particle-containing layer is preferably a to 10a, more preferably 2a to 8a, and more preferably 1a to 1a, where a is the thickness of the hexagonal or circular plate-like metal particles. Particularly preferred is 5a.

Here, the thickness of each layer of the metal particle-containing layer can be measured from, for example, an image obtained by SEM observation of a cross-sectional sample of the infrared shielding film.
Moreover, even when it has other layers, such as an overcoat layer mentioned later, on the said metal particle content layer of an infrared shielding film, the boundary of another layer and the said metal particle content layer is determined by the same method. And the thickness d of the metal particle-containing layer can be determined. When coating the metal particle-containing layer using the same type of polymer as the polymer contained in the metal particle-containing layer, the boundary between the metal particle-containing layer and the metal particle-containing layer is usually determined by an SEM observation image. And the thickness d of the metal particle-containing layer can be determined.

[1-2-10. Method for synthesizing tabular metal grains]
The method for synthesizing the metal tabular grains is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a liquid phase method such as a chemical reduction method, a photochemical reduction method, an electrochemical reduction method, etc. It is mentioned as what can synthesize circular flat metal particles. Among these, a liquid phase method such as a chemical reduction method or a photochemical reduction method is particularly preferable in terms of shape and size controllability. After synthesizing hexagonal to triangular metal tabular grains, hexagonal to triangular tabular metal grains can be obtained by, for example, etching treatment with a dissolved species that dissolves silver such as nitric acid and sodium sulfite, and aging treatment by heating. The flat metal particles having a hexagonal shape or a circular shape may be obtained.

As a method for synthesizing the metal tabular grains, in addition to the above, a seed crystal may be previously fixed on the surface of a transparent substrate such as a film or glass, and then metal grains (for example, Ag) may be grown in a tabular form.

In the infrared shielding film of the present invention, the metal tabular grain may be subjected to further treatment in order to impart desired characteristics. The further treatment is not particularly limited and may be appropriately selected depending on the purpose. For example, the formation of a high refractive index shell layer, the addition of various additives such as a dispersant and an antioxidant may be included. Can be mentioned.

-1-2-10-1. Formation of high refractive index shell layer
In order to further improve the visible light region transparency, the metal tabular grain may be coated with a high refractive index material having high visible light region transparency.
As the high refractive index material is not particularly limited and may be appropriately selected depending on the purpose, for _example, TiO _x, BaTiO _3, ZnO, etc. SnO _2, ZrO _2, NbO _x and the like.

There is no restriction | limiting in particular as said coating method, According to the objective, it can select suitably, For example, Langmuir, 2000, 16 volumes, p. As reported in 2731-2735, a method of forming a TiO _x layer on the surface of silver metal tabular grains by hydrolyzing tetrabutoxy titanium may be used.

In addition, when it is difficult to form a high refractive index metal oxide layer shell directly on the metal tabular grain, after synthesizing the metal tabular grain as described above, an SiO ₂ or polymer shell layer is appropriately formed, The metal oxide layer may be formed on the shell layer. When TiO _x is used as a material for the high refractive index metal oxide layer, since TiO _x has photocatalytic activity, there is a concern of deteriorating the matrix in which the metal tabular grains are dispersed. After forming the TiO _x layer on the tabular grains, an SiO ₂ layer may be appropriately formed.

-1-2-10-2. Addition of various additives-
In the infrared shielding film of the present invention, when the metal particle-containing layer contains a polymer and the main polymer of the polymer is a polyester resin, it is preferable to add a crosslinking agent from the viewpoint of film strength. The crosslinking agent is not particularly limited, and examples thereof include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Of these, carbodiimide and oxazoline crosslinking agents are preferred. Specific examples of the carbodiimide-based crosslinking agent include, for example, Carbodilite V-02-L2 (manufactured by Nisshinbo Industries, Inc.). It is preferable to contain 1 to 20% by mass of a crosslinking agent-derived component with respect to the total binder in the metal particle-containing layer, and more preferably 2 to 20% by mass.
Moreover, in the infrared shielding film of this invention, when the said metal particle content layer contains a polymer, it is preferable from a viewpoint from which generation | occurrence | production of a repelling is suppressed and a favorable planar layer is obtained. Examples of surfactants that can be used as the surfactant include known anionic and nonionic surfactants such as Lapisol A-90 (manufactured by NOF Corporation), Narrow Acty HN-100 (manufactured by Sanyo Chemical Industries) is available. The surfactant is preferably contained in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total binder in the metal particle-containing layer.

The metal tabular grains may adsorb an antioxidant such as mercaptotetrazole or ascorbic acid in order to prevent oxidation of metals such as silver constituting the metal tabular grains. Further, an oxidation sacrificial layer such as Ni may be formed on the surface of the metal tabular grain for the purpose of preventing oxidation. Further, it may be covered with a metal oxide film such as SiO ₂ for the purpose of blocking oxygen.
For the purpose of imparting dispersibility, the metal tabular grain is, for example, a low molecular weight dispersant or a high molecular weight dispersant containing at least one of N elements such as quaternary ammonium salts and amines, S elements, and P elements. A dispersant may be added.

<Support>
The infrared shielding film of the present invention preferably has a support.
There is no restriction | limiting in particular as said support body, A well-known support body can be used.
The support is not particularly limited as long as it is an optically transparent support and can be appropriately selected according to the purpose. For example, the visible light transmittance is 70% or more, preferably 80% or more. And those with high transmittance in the near infrared region.
There is no restriction | limiting in particular about the shape, a structure, a magnitude | size, material, etc. as said support body, According to the objective, it can select suitably. Examples of the shape include a flat plate shape, and the structure may be a single layer structure or a laminated structure, and the size may be the size of the infrared shielding film. It can be appropriately selected according to the above.
The material for the support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1, polybutene-1, polyethylene terephthalate, Polyester resins such as polyethylene naphthalate; polycarbonate resins, polyvinyl chloride resins, polyphenylene sulfide resins, polyether sulfone resins, polyethylene sulfide resins, polyphenylene ether resins, styrene resins, acrylic resins, polyamides Examples thereof include a film made of a cellulose resin such as a cellulose resin, a polyimide resin, and cellulose acetate, or a laminated film thereof. Among these, a polyethylene terephthalate film is particularly preferable.
The thickness of the support is not particularly limited and can be appropriately selected depending on the purpose of use of the infrared shielding film. Usually, the thickness is about 10 μm to 500 μm, but it is thinner from the viewpoint of the demand for thinning. preferable. The thickness of the support is preferably 10 μm to 100 μm, more preferably 20 to 75 μm, and particularly preferably 35 to 75 μm. When the thickness of the support is sufficiently thick, adhesion failure tends to hardly occur. Moreover, when the thickness of the said support body is thin enough, when it bonds together to a building material or a motor vehicle as an infrared shielding film, there exists a tendency for the construction as it is not too strong and to be constructed easily. Furthermore, when the support is sufficiently thin, the visible light transmittance is increased, and the raw material cost tends to be suppressed.

<Dye-containing layer>
The infrared shielding film of the present invention is characterized by containing a compound having absorption in the infrared region. Hereinafter, a layer containing a compound having absorption in the infrared region is also referred to as a dye-containing layer. In addition, a pigment | dye content layer may fulfill | perform the role of another functional layer.

The absorption peak wavelength of the compound having absorption in the infrared region is preferably shorter than the reflection peak wavelength of the metal particles from the viewpoint of efficiently shielding heat rays.

In the infrared shielding film of the present invention, the layer containing a compound having absorption in the infrared region preferably contains 20 to 190 mg / m ^{2 of the} compound having absorption in the infrared region. The planar shape of an infrared shielding film can be improved by making the pigment | dye contained in the said pigment | dye content layer into the range of 190 mg / m < ² > or less. As a method for controlling the pigment contained in the pigment-containing layer within this range, a method of adjusting the pigment coating amount when forming the pigment-containing layer by coating can be used.
The upper limit of the content of the dye contained in the dye-containing layer is preferably 150 mg / m ² or less from the viewpoint of improving the surface shape, and 120 mg / m ² or less is the maximum reflection of the infrared shielding film. From the viewpoint of increasing the rate and suppressing the transmittance at the maximum reflection wavelength, it is particularly preferably 100 mg / m ² or less.
On the other hand, the lower limit of the content of the dye contained in the dye-containing layer is 10 mg / m ² or more in view of increasing the maximum reflectance of the infrared shielding film and suppressing the transmittance at the maximum reflection wavelength. From the same viewpoint, it is more preferably 20 mg / m ² or more, and particularly preferably 30 mg / m ² or more from the same viewpoint.

The density of the dye in the dye-containing layer is preferably 0.25 g / cm ³ or more from the viewpoint of lowering the transmittance at the maximum reflection wavelength and lowering the warming rate, and is 0.30 to 1.0 g / cm 3. ³ is more preferable, 0.40 to 0.90 g / cm ³ is particularly preferable, and 0.50 to 0.70 g / cm ³ is particularly preferable.

(Configuration of dye-containing layer)
In the infrared shielding film of the present invention, the thickness of the dye-containing layer is preferably 200 nm or less from the viewpoint of improving the surface state, more preferably 50 to 200 nm, and most preferably 100 to 200 nm. This is particularly preferable from the viewpoint of increasing the transmittance and reducing the transmittance at the maximum reflection wavelength.

The dye-containing layer may be disposed adjacent to the support or may be disposed via another layer therebetween. The dye-containing layer is preferably a layer disposed adjacent to the support, a layer disposed adjacent to the metal particle-containing layer, or the metal particle-containing layer. .

(Dye)
There is no restriction | limiting in particular as said pigment | dye, A well-known pigment | dye can be used. Examples of the pigment include dyes and pigments.
The pigment is not particularly limited, and a known pigment can be used. For example, pigments described in JP-A-2005-17322, [0032] to [0039] and the like can be mentioned.
There is no restriction | limiting in particular in the said dye, A well-known dye can be used. Dyes that can be stably dissolved or dispersed in an aqueous dispersion of the polymer are preferred, and these dyes preferably have a water-soluble group. Examples of the water-soluble group include a carboxyl group and a salt thereof, a sulfo group and a salt thereof. In addition, water-soluble dyes such as cyanine dyes and barbituric acid oxonol dyes described below can be applied as aqueous solutions without dissolving them in organic solvents. preferable. These dyes are preferably used as aggregates, and particularly preferably used as J aggregates. By using a J-aggregate, it becomes easy to set the absorption wavelength of a dye having an absorption maximum in the visible region in a desired near-infrared region in a non-association state. Moreover, durability, such as heat resistance of a dye, heat-and-moisture resistance, and light resistance, can be improved. It is also a preferred form to adjust the water solubility of these dyes so that they are hardly soluble or insoluble, or in other words, to be used as lake dyes. Thereby, durability, such as heat resistance of a dye, heat-and-moisture resistance, and light resistance, can be improved, and it is preferable.

In the infrared shielding film of the present invention, the dye is preferably an infrared absorbing dye from the viewpoint of selectively reflecting heat rays (near infrared rays).
Examples of the infrared absorbing dye include a near infrared absorbing dye described in JP-A-2008-181096, JP-A-2001-228324, JP-A-2009-244493, and the like, and JP-A 2010-90313. Near infrared absorbing compounds and the like can be preferably used.
Examples of the infrared absorbing pigment include cyanine dyes, oxonol dyes, and pyrrolopyrrole compounds.

In the infrared shielding film of the present invention, the compound having absorption in the infrared region is preferably a compound represented by the following general formula (1) or a compound represented by the following general formula (2). A pyrrolopyrrole compound represented by the formula (2) is more preferable from the viewpoint of improving fastness and improving storage stability.

(In General Formula (2), R ^1a and R ^1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R ² and R ³ each independently represent a hydrogen atom. Or at least one is an electron-withdrawing group, and R ² and R ³ may combine to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted group Represents a boron or metal atom, and may be a covalent bond or a coordinate bond with at least one group of R ^1a , R ^1b and R ^3. )

The preferred range of the compound represented by the general formula (1) is the same as the preferred range of the general formula (I) in JP-A-2001-228324.
The preferred range of the compound represented by the general formula (2) is the same as the preferred range of the general formula (1) in JP-A-2009-263614.

(1) Cyanine dye The cyanine dye is preferably a methine dye such as a pentamethine cyanine dye, a heptamethine cyanine dye, or a nonamethine cyanine dye, and a methine dye described in JP-A-2001-228324 is preferred. As the cyclic group of the cyanine dye, those having a thiazole ring, an indolenine ring or a benzoindolenine ring are preferable.

Examples of the cyanine dye used in the present invention include the cyanine dye represented by the general formula (1), that is, the general formula (I) of JP-A-2001-228324, and among them, a pentamethine cyanine dye. Heptamethine cyanine dyes or nonamethine cyanine dyes (especially their aggregates) are preferred, and pentamethine cyanine dye, heptamethine cyanine dye or nonamethine cyanine represented by the general formula (II) of JP-A No. 2001-228324 Dyes (particularly, aggregates thereof) are more preferable, and heptamethine cyanine dyes represented by the general formula (II) in JP-A-2001-228324 are particularly preferable.

Specific examples of the heptamethine cyanine dye represented by the general formula (II) of JP-A-2001-228324 among the compounds represented by the general formula (1) are shown below. It is not limited to examples.

(2) Oxonol Dye The oxonol dye is preferably an oxonol dye represented by the general formula (II) of JP-A No. 2009-244493, and more preferably a barbituric acid oxonol dye having a barbituric acid ring.
Examples of oxonol dyes represented by the general formula (II) in JP-A-2009-244493 are shown below, but the present invention is not limited to the following specific examples.

(3) The pyrrolopyrrole compound As the pyrrolopyrrole compound, the pyrrolopyrrole compound represented by the above general formula (2), that is, the general formula (1) of JP2009-263614A or JP2010-90313A is exemplified. A pyrrolopyrrole compound represented by any one of the general formulas (2), (3), and (4) described in JP-A-2009-263614 and 2010-90313 is more preferable.

Hereinafter, the pyrrolopyrrole compound (dye) represented by the general formula (2), that is, any one of the general formulas (1) to (4) in JP2009-263614A and JP2010-90313A is described below. Specific examples will be shown, but the present invention is not limited to the following specific examples.

(polymer)
The infrared shielding film of the present invention preferably contains a polymer in the dye-containing layer. The polymer can be used as a so-called binder in the dye-containing layer.
In the infrared shielding film of the present invention, the mass ratio of the polymer to the dye (polymer / dye ratio) in the dye-containing layer is 5 or less to reduce the transmittance at the maximum reflection wavelength and to reduce the warming rate. From the viewpoint of The mass ratio of the polymer to the dye in the dye-containing layer is more preferably 0.1 to 4, particularly preferably 0.2 to 3.0, and preferably 0.5 to 3.0. More particularly preferred.

The preferred range of the content of the polymer contained in the dye-containing layer is also related to the preferred range of the mass ratio of the polymer to the dye, but is preferably 350 mg / m ² or less, for example, from a planar viewpoint, It is preferable from a viewpoint of contact | adherence with a support body that it is 30 mg / m < ² > or more.

The type of the polymer is not particularly limited, and a known polymer can be used, and a transparent polymer is more preferable. Examples of the polymer include polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethyl methacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin, and cellulose. And polymers such as natural polymers. Among them, in the infrared shielding film of the present invention, the polymer is preferably polyester, polyurethane, or polyacrylate resin, and polyester is more preferable from the viewpoint of adhesion to the support.

In the infrared shielding film of the present invention, it is preferable that the polymer is an aqueous dispersion from the viewpoint of environmental influence and the reduction of coating cost.

In the present invention, as the polymer, Plus Coat Z-592 (manufactured by Kyoyo Chemical Co., Ltd.), which is a water-soluble polyester resin, can be preferably used.

<Other layers and ingredients>
<< Adhesive layer >>
The infrared shielding film of the present invention preferably has a pressure-sensitive adhesive layer (hereinafter also referred to as a pressure-sensitive adhesive layer). The adhesive layer may include an ultraviolet absorber.
The material that can be used for forming the adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl butyral (PVB) resin, acrylic resin, styrene / acrylic resin, urethane resin, polyester Examples thereof include resins and silicone resins. These may be used individually by 1 type and may use 2 or more types together. An adhesive layer made of these materials can be formed by coating.
Furthermore, an antistatic agent, a lubricant, an antiblocking agent and the like may be added to the adhesive layer.
The thickness of the adhesive layer is preferably 0.1 μm to 10 μm.

<< Hard coat layer >>
In order to add scratch resistance, it is also preferable that the functional film includes a hard coat layer having hard coat properties. The hard coat layer can contain metal oxide particles.
There is no restriction | limiting in particular as said hard-coat layer, The kind and formation method can be selected suitably according to the objective, For example, acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin And thermosetting or photocurable resins such as fluorine-based resins. The thickness of the hard coat layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm to 50 μm. When an antireflection layer and / or an antiglare layer are further formed on the hard coat layer, a functional film having antireflection properties and / or antiglare properties in addition to scratch resistance is preferably obtained. The hard coat layer may contain the metal oxide particles.

<< Overcoat layer >>
In the infrared shielding film of the present invention, in order to prevent oxidation and sulfidation of the metal tabular grains due to mass transfer and to provide scratch resistance, the infrared shielding film of the present invention has the hexagonal or circular tabular metal particles. You may have the overcoat layer closely_contact | adhered to the surface of the said exposed metal particle content layer. Moreover, you may have an overcoat layer between the said metal particle content layer and the below-mentioned ultraviolet absorption layer. Infrared shielding film of the present invention, especially when the metal tabular grains are unevenly distributed on the surface of the metal particle-containing layer, prevention of contamination of the manufacturing process due to the peeling of the metal tabular grains, prevention of disordered arrangement of the metal tabular grains at the time of coating another layer, For example, an overcoat layer may be provided.
The overcoat layer may contain an ultraviolet absorber. The overcoat layer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, the overcoat layer contains a binder, a matting agent, and a surfactant, and further contains other components as necessary. It becomes. The binder is not particularly limited and may be appropriately selected depending on the purpose. For example, thermosetting of acrylic resin, silicone resin, melamine resin, urethane resin, alkyd resin, fluorine resin, etc. Mold or photo-curable resin. The thickness of the overcoat layer is preferably 0.01 μm to 1,000 μm, more preferably 0.02 μm to 500 μm, particularly preferably 0.1 to 10 μm, and particularly preferably 0.2 to 5 μm.

<< Undercoat layer >>
On the other hand, in the infrared shielding film of the present invention, an undercoat layer may be provided between the support and the metal particle-containing layer. The undercoat layer is not particularly limited and may be appropriately selected depending on the purpose, but may be a layer containing a compound having absorption in the infrared region, and may be a compound having absorption in the infrared region. A preferable composition and thickness in the case where the layer is not an included layer are the same as the preferable composition and thickness of the overcoat layer. A plurality of the undercoat layers may be provided. In that case, it is preferable to provide only one layer containing a compound having absorption in the infrared region, and only one layer is provided on the side in contact with the support. It is more preferable.

<< Backcoat layer >>
On the other hand, the infrared shielding film of the present invention may have a back coat layer on the surface of the support opposite to the metal particle-containing layer. The backcoat layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, the backcoat layer may be a layer containing a compound having absorption in the infrared region, or may be a metal oxide particle-containing layer described later. However, the preferred composition and thickness in the case of a layer containing a compound having absorption in the infrared region or a metal oxide particle-containing layer described later are the same as the preferred composition and thickness of the overcoat layer.

<< UV absorber >>
The infrared shielding film of the present invention preferably has a layer containing an ultraviolet absorber.
The layer containing the ultraviolet absorber can be appropriately selected depending on the purpose, and may be an adhesive layer, or a layer (for example, an overcoat) between the adhesive layer and the metal particle-containing layer. Layer). In any case, it is preferable that the ultraviolet absorber is added to a layer disposed on the side irradiated with sunlight with respect to the metal particle-containing layer.

The ultraviolet absorber is not particularly limited and may be appropriately selected depending on the purpose. For example, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a salicylate ultraviolet absorber, Examples include cyanoacrylate ultraviolet absorbers. These may be used individually by 1 type and may use 2 or more types together.

The benzophenone-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2,4droxy-4-methoxy-5-sulfobenzophenone.

The benzotriazole ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2- (5-chloro-2H-benzotriazol-2-yl) -4-methyl-6 -Tert-butylphenol (tinuvin 326), 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tertiarybutylphenyl) benzotriazole, 2- (2-hydroxy-3- 5-ditertiary butylphenyl) -5-chlorobenzotriazole and the like.

The triazine-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include mono (hydroxyphenyl) triazine compounds, bis (hydroxyphenyl) triazine compounds, and tris (hydroxyphenyl) triazine compounds. Etc.
Examples of the mono (hydroxyphenyl) triazine compound include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl). Phenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-isooctyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis ( 2,4-dimethylphenyl) -1,3,5-triazine, etc. Is mentioned. Examples of the bis (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-Bis (2-hydroxy-3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-hexyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2-phenyl-4,6-bis [2-hydroxy-4- [3- (methoxyheptaethoxy ) -2-hydroxypropyloxy] phenyl] -1,3,5-triazine and the like. Examples of the tris (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2 , 4,6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropyloxy) ) Phenyl] -1,3,5-triazine, 2,4-bis [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -6- (2,4-dihydroxyphenyl) -1 , 3,5-triazine, 2,4,6-tris [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -1,3,5-triazine, 2,4-bis [2 -Hydroxy-4- [1- (isooctyloxy) Carbonyl) ethoxy] phenyl] -6- [2,4-bis [1- (iso-octyloxy) ethoxy] phenyl] -1,3,5-triazine.

The salicylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, Examples include 2-ethylhexyl salicylate.

The cyanoacrylate-based ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3 , 3-diphenyl acrylate and the like.

The binder is not particularly limited and may be appropriately selected depending on the intended purpose, but preferably has higher visible light transparency and higher solar transparency, and examples thereof include acrylic resin, polyvinyl butyral, and polyvinyl alcohol. . When the binder absorbs heat rays, the reflection effect of the metal tabular grains is weakened. Therefore, the ultraviolet absorbing layer formed between the heat ray source and the metal tabular grains is absorbed in the region of 450 nm to 1,500 nm. It is preferable to select a material that does not have a thickness, or to reduce the thickness of the ultraviolet absorbing layer.
The thickness of the ultraviolet absorbing layer is preferably 0.01 μm to 1,000 μm, more preferably 0.02 μm to 500 μm. When the thickness is less than 0.01 μm, ultraviolet absorption may be insufficient, and when it exceeds 1,000 μm, the visible light transmittance may be reduced.
The content of the ultraviolet absorbing layer varies depending on the ultraviolet absorbing layer to be used and cannot be generally defined, but it is preferable to appropriately select a content that gives a desired ultraviolet transmittance in the infrared shielding film of the present invention.
The ultraviolet transmittance is preferably 5% or less, and more preferably 2% or less. When the ultraviolet transmittance exceeds 5%, the color of the metal tabular grain layer may change due to ultraviolet rays of sunlight.

<< Metal oxide particles >>
In order to absorb long wave infrared rays, the infrared ray shielding film of the present invention is preferable from the viewpoint of balance between heat ray shielding and production cost even if it contains at least one kind of metal oxide particles. In this case, for example, the overcoat layer 5 preferably contains metal oxide particles. The overcoat layer 5 may be laminated with the metal oxide particle-containing layer 2 via the substrate 1. When the infrared shielding film of this invention is arrange | positioned so that the metal tabular grain content layer 2 may become the incident direction side of heat rays, such as sunlight, a part (or all) of heat ray may be in the metal tabular grain content layer 2. After the reflection, a part of the heat ray is absorbed by the overcoat layer 5, and the amount of heat directly received inside the infrared ray shielding film due to the heat ray that is not absorbed by the metal oxide containing layer 2 and is transmitted through the infrared ray shielding film. And the calorie | heat amount as the sum total of the calorie | heat amount absorbed by the metal oxide content layer 2 of an infrared shielding film and transmitted indirectly inside an infrared shielding film can be reduced.
There is no restriction | limiting in particular as a material of the said metal oxide particle, According to the objective, it can select suitably, For example, a tin dope indium oxide (henceforth "ITO"), a tin dope antimony oxide (henceforth). , Abbreviated as “ATO”), zinc oxide, titanium oxide, indium oxide, tin oxide, antimony oxide, glass ceramics, and the like. Among these, ITO, ATO, and zinc oxide are more preferable, and infrared rays having a wavelength of 1,200 nm or more are applied in that they are excellent in heat ray absorption ability and can produce an infrared shielding film having a wide range of heat ray absorption ability when combined with metal tabular grains. In particular, ITO is preferable in that it has a visible light transmittance of 90% or more.
The volume average particle size of the primary particles of the metal oxide particles is preferably 0.1 μm or less in order not to reduce the visible light transmittance.
There is no restriction | limiting in particular as a shape of the said metal oxide particle, According to the objective, it can select suitably, For example, spherical shape, needle shape, plate shape, etc. are mentioned.

The content of the metal oxide particles in the metal oxide particle-containing layer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 0.1 g / m ² to 20 g / m ² , 0.5 g / m ² to 10 g / m ² is more preferable, and 1.0 g / m ² to 4.0 g / m ² is more preferable.
If the content is less than 0.1 g / m ² , the amount of solar radiation felt on the skin may increase, and if it exceeds 20 g / m ² , the visible light transmittance may deteriorate. On the other hand, when the content is 1.0 g / m ² to 4.0 g / m ^2, it is advantageous in that the above two points can be avoided.
The content of the metal oxide particles in the metal oxide particle-containing layer is, for example, from the observation of the super foil section TEM image and surface SEM image of the heat ray shielding layer, and the number of metal oxide particles in a certain area and It can be calculated by measuring the average particle diameter and dividing the mass (g) calculated based on the number and average particle diameter and the specific gravity of the metal oxide particles by the constant area (m ² ). . Further, metal oxide fine particles in a certain area of the metal oxide particle-containing layer are eluted in methanol, and the mass (g) of the metal oxide fine particles measured by fluorescent X-ray measurement is divided by the constant area (m ² ). This can also be calculated.

<Method for producing infrared shielding film>
The method for producing the infrared shielding film of the present invention is not particularly limited and can be appropriately selected according to the purpose.For example, a dispersion having the dye on the surface of the lower layer such as the support, Examples thereof include a method of coating by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, and the like, and a method of surface orientation by a method such as an LB film method, a self-organization method, and spray coating. The dye-containing layer is preferably formed by coating. That is, the dye-containing layer is preferably a dye coating layer. Among them, the method of applying with a bar coater is preferable.

When the dye-containing layer is formed by coating, other additives such as a solvent and a surfactant may be added to the coating solution in addition to the dye and the polymer.

The solvent is not particularly limited and water or a known organic solvent can be used. For example, water, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, acetone, methyl alcohol, N-propyl alcohol, 1-propyl alcohol, Various things such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, ethyl lactate, methyl lactate, and caprolactam can be used. In the present invention, it is preferable to use an aqueous solvent from the viewpoint of environmental influence and the point of reducing coating cost.
The solvent may be used in combination of two or more, in addition to being used alone. In the present invention, specifically, it is more preferable to use as an aqueous solvent in which water and methanol are combined.

Examples of other additives include surfactants and additives described in paragraph numbers [0027] to [0031] of JP-A-2005-17322.
The surfactant is not particularly limited, but may be any of aliphatic, aromatic, and fluorine surfactants, and may be any nonionic, anionic, or cationic surfactant. Examples of the surfactant include those described in JP 2011-218807 A.
As the surfactant, specifically, Rapisol A-90 manufactured by NOF Corporation, Aronacty CL95 manufactured by Sanyo Chemical Industries, Ltd., and the like are preferably used.
The surfactants may be used in combination of two or more in addition to being used alone.

When the dye-containing layer is formed by coating, preferred ranges of the dye coating amount and the polymer coating amount are the same as the preferred ranges of the dye content and the polymer content contained in the dye-containing layer, respectively. is there.

In the case of forming the dye-containing layer by coating, it is preferable to form the dye-containing layer by applying the coating solution and then drying and solidifying by a known method. As a drying method, drying by heating is preferable.

-1. Method for forming metal particle-containing layer
The method for forming the metal particle-containing layer of the present invention is not particularly limited and may be appropriately selected depending on the purpose. For example, a dispersion having the metal tabular particles on the surface of the lower layer such as the substrate. May be applied by a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like, or may be subjected to surface orientation by a method such as an LB film method, a self-organization method, or spray coating. When the infrared shielding film of the present invention is produced, the composition of the metal particle-containing layer used in the examples described later is used, and by adding latex or the like, the hexagonal or circular tabular metal particles 80 The number% or more is made to exist in the range of d / 2 from the surface of the metal particle-containing layer. It is preferable that 80% by number or more of the metal tabular grains of the hexagonal or circular tabular metal particles exist in a range of d / 3 from the surface of the metal particle-containing layer. The amount of the latex added is not particularly limited, but for example, it is preferable to add 1 to 10000 mass% with respect to the metal tabular grains.

In addition, in order to promote plane orientation, after applying metal tabular grains, it may be promoted by passing through a pressure roller such as a calender roller or a lami roller.

-2. Formation method of overcoat layer
The overcoat layer is preferably formed by coating. The coating method at this time is not particularly limited, and a known method can be used. For example, a dispersion containing the ultraviolet absorber can be used as a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like. The method of apply | coating by etc. is mentioned.

-3. Formation method of hard coat layer
The hard coat layer is preferably formed by coating. The coating method at this time is not particularly limited, and a known method can be used. For example, a dispersion containing the ultraviolet absorber can be used as a dip coater, a die coater, a slit coater, a bar coater, a gravure coater, or the like. The method of apply | coating by etc. is mentioned.

-4. Formation method of adhesive layer
The adhesive layer is preferably formed by coating. For example, it can be laminated on the surface of the lower layer such as the substrate, the metal particle-containing layer, or the ultraviolet absorbing layer. There is no limitation in particular as the coating method at this time, A well-known method can be used.

<Application>
-Adhesive layer lamination by dry lamination-
When using the infrared shielding film film of the present invention to provide functionality to existing window glass, an adhesive is laminated and adhered to the indoor side of the glass. In that case, it is better to laminate the adhesive layer on the silver nanodisk particle layer and paste it from the surface to the window glass, because the reflective layer facing the sunlight side will prevent heat generation as much as possible. It is.
When laminating the pressure-sensitive adhesive layer on the surface of the silver nanodisk layer, a coating solution containing a pressure-sensitive adhesive can be applied directly to the surface, but various additives, plasticizers and solvents used in the pressure-sensitive adhesive However, in some cases, the arrangement of the silver nanodisk layer may be disturbed, or the silver nanodisk itself may be altered. In order to minimize such harmful effects, a film is prepared by previously applying and drying an adhesive on a release film, and the adhesive surface of the film and the silver nanodisk layer surface of the film of the present invention are prepared. It is effective to laminate in a dry state.
The infrared shielding film of this invention may be used independently as a heat ray shielding material, and may be laminated | stacked with another functional layer. Further, the infrared shielding film of the present invention may be a bonded structure bonded to glass or the like.
If the infrared shielding film of this invention is an aspect used in order to selectively reflect (absorb as needed) a heat ray (near infrared rays), there will be no restriction | limiting in particular, What is necessary is just to select suitably according to the objective. Examples of the film include a vehicle film and a laminated structure, a building material film and a laminated structure, and an agricultural film. Among these, in terms of energy saving effect, a vehicle film and a laminated structure, a building material film and a laminated structure are preferable.
In the present invention, heat rays (near infrared rays) mean near infrared rays (780 nm to 1,800 nm) contained in sunlight by about 50%.

The features of the present invention will be described more specifically with reference to the following examples.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Comparative Example 1]
-Synthesis of tabular metal grains-
In a reaction kettle, 24.5 mL of 1% aqueous sodium citrate solution and 16.7 mL of 8 g / L aqueous sodium polystyrene sulfonate solution were added to 308 mL of pure water and heated to 35 ° C. To this solution, 1 mL of 2.3 mM aqueous sodium borohydride solution was added, and 363 mL of 0.5 mM aqueous silver nitrate solution (Ag-1) was added with stirring. After stirring this solution for 30 minutes, 24.5 mL of 1% sodium citrate aqueous solution and 33 mL of 10 mM aqueous ascorbic acid solution and 211 mL of pure water were added to this solution. To this solution, 199 mL of 0.5 mM aqueous silver nitrate solution (Ag-2) was further added with stirring. After stirring for 30 minutes, 197 mL of a 7.7% aqueous potassium hydroquinone sulfonate solution, 33 g of inert gelatin having an average molecular weight of 100,000 and 22 g of inert gelatin having an average molecular weight of 20,000 were dissolved in 480 mL of pure water. To the medium solution. Next, 4.4 mL of 1N nitric acid was added to the solution. Thereafter, a white precipitate mixed solution of silver sulfite obtained by mixing 67 mL of 13.5% aqueous sodium sulfite solution, 228 mL of 10% aqueous silver nitrate solution and 369 mL of pure water was added to this solution in advance. After stirring this solution for 300 minutes, 145 mL of 1N NaOH was added, and silver tabular grain dispersion liquid A1 was obtained.

-Evaluation of metal particles-
(Ratio of tabular grains, average grain diameter (average equivalent circle diameter), coefficient of variation)
SEM images of 400 grains in this silver tabular grain dispersion A1 were observed, and image analysis was performed with A as the tabular grains mainly composed of hexagonal shapes and B as the other irregular shaped grains. The ratio of the number of tabular grains (number%) was 96%. The average particle size of the tabular grains corresponding to A was (average equivalent circle diameter) 135 nm. The average equivalent circle diameter (coefficient of variation) of the tabular grains A obtained by dividing the standard deviation of the particle size distribution by the average equivalent circle diameter was 17%.

(Average particle thickness)
The obtained silver tabular grain dispersion A1 is dropped on a glass substrate and dried, and the thickness of each metal tabular grain corresponding to A is measured by an atomic force microscope (AFM) (Nanocute II, manufactured by Seiko Instruments Inc.). It measured using. The measurement conditions using the AFM were a self-detecting sensor, DFM mode, a measurement range of 5 μm, a scanning speed of 180 seconds / frame, and a data point of 256 × 256. The average grain thickness of the tabular grains corresponding to A in the silver tabular grain dispersion A1 was 10 nm.

500 mL of the silver tabular grain dispersion liquid A1 was centrifuged at 7,000 rpm for 30 minutes in a centrifuge (Hoku200, manufactured by Kokusan Co., Ltd., Amble Rotor BN) to precipitate silver tabular grains. The supernatant liquid 450 mL after centrifugation was discarded, 200 mL of 0.2 mM NaOH aqueous solution was added, the precipitated hexagonal silver tabular grain was redispersed, and silver tabular grain dispersion liquid B1 was prepared.
Further, the following compound was added to the silver tabular grain dispersion liquid B1 to prepare a coating liquid M1 for a metal particle-containing layer.

-Preparation of metal particle containing layer-
(Preparation of coating solution M1 for the metal particle-containing layer)
A coating solution M1 for a metal particle-containing layer having the composition shown below was prepared.
Composition of coating liquid M1 for the metal particle-containing layer:
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration: 30% by mass) 0.27 parts by mass Surfactant A: F Ripar 8780P
(Made by Lion Co., Ltd., solid content 1% by mass) 0.96 parts by mass Surfactant B: Aronactee CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content: 1% by mass) 1.19 parts by mass Silver tabular particle dispersion B1 26.6 parts by mass 1- (5-methylureidophenyl) -5-mercaptotetrazole (Wako Pure Chemical ( Co., Ltd., solid content 2% by mass) 0.61 parts by mass water 44.87 parts by mass methanol 30 parts by mass

(Preparation of coating solution U1 for coating layer U1)
A coating solution U1 for the coating layer U1 having the composition shown below was prepared.
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration 30% by mass) 1.83 parts by mass Binder polymer: Pluscoat Z-592
(Solid Chemical Industries, Ltd., solid content 25%) 3.3 parts by mass Surfactant B: Aronactee CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.18 parts by mass water 64.63 parts by mass IPA 25.94 parts by mass

(Preparation of coating film 1)
On the surface of a PET film (A4300, manufactured by Toyobo Co., Ltd., thickness: 75 μm), the coating liquid U1 for the coating layer U1 is used as a U1 layer so that the average thickness after drying becomes 100 nm using a wire bar. Applied. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and formed U1 layer.
Furthermore, the coating liquid M1 for metal particle content layers was apply | coated so that the average thickness after drying might be set to 20 nm on the U1 layer using the wire bar. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and produced the coating film 1 for infrared shielding films of the comparative example 1.

[Example 2]
-Preparation of aqueous dye dispersion BD-10-
Water was added to 3 parts by mass of pyrrolopyrrole dye (D-10) having the structure shown below and 2 parts by mass of DisperBYK2091 (manufactured by Big Chemie) to make 100 parts by mass. Further, 50 parts by mass of 0.1 mmφ zirconia beads were added, and the mixture was treated with a planetary ball mill at 300 rpm for 5 hours to prepare an aqueous dye dispersion BD-10 composed of pyrrolopyrrole dye (D-10) fine particles. did. Thereafter, beads were separated and removed from the water product by filtration. When the obtained fine particles were observed with an electron microscope, they were irregular fine particles having an average particle diameter of 40 nm.

-Preparation of coating liquid D10 for dye dispersion-containing layer D10-
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration 30% by mass) 1.83 parts by mass Binder polymer: Pluscoat Z-592
(Solid Chemical Industries, Ltd., solid content 25%) 3.3 parts by mass Surfactant B: Aronactee CL-95
(Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.18 parts by mass Dye aqueous dispersion BD-10 25.0 parts by mass Water 39.63 parts by mass IPA 25.94 parts by mass

-Preparation of coating solution M0 for a layer not containing metal particles-
A coating solution M0 for a layer not containing metal particles having the composition shown below was prepared.
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration: 30% by mass) 0.27 parts by mass Surfactant A: F Ripar 8780P
(Made by Lion Co., Ltd., solid content 1% by mass) 0.96 parts by mass Surfactant B: Aronactee CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.19 parts by mass 1% inert gelatin aqueous solution 32.74 parts by mass 1- (5-methylureidophenyl) -5-mercaptotetrazole (Wako Pure Chemical ( Co., Ltd., solid content 2% by mass) 0.61 parts by mass water 34.23 parts by mass methanol 30 parts by mass

-Production of coating film 2-
On the surface of a PET film (A4300 manufactured by Toyobo Co., Ltd., thickness: 75 μm), the coating liquid D10 for the pigment dispersion-containing layer is applied to the pigment D-10 coating amount to 60 mg / m ² using a wire bar. It was applied as follows. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and formed D10 layer.
Further, on the D10 layer, a coating liquid M0 for a layer not containing metal particles was applied using a wire bar so that the average thickness after drying was 20 nm.
Then, it heated at 130 degreeC for 1 minute, dried and solidified, and produced the coating film 2 for infrared shielding films of the comparative example 2.

[Example 1]
-Production of coating film 3-
On the surface of a PET film (Toyobo Co., Ltd. A4300, thickness: 75 μm), the coating solution D10 was applied using a wire bar so that the coating amount of the dye D-10 was 60 mg / m ² . Then, it heated at 130 degreeC for 1 minute, dried and solidified, and formed D10 layer.
On the obtained D10 layer, the coating liquid M1 was applied using a wire bar so that the average thickness after drying was 20 nm.
Then, it heated at 130 degreeC for 1 minute, dried and solidified, and produced the coating film 3 for infrared shielding films of Example 1.

[Comparative Example 3]
-Production of coating film 4-
On the surface of a PET film (Toyobo Co., Ltd. A4300, thickness: 75 μm), the coating liquid U1 was applied using a wire bar so that the average thickness after drying was 100 nm. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and formed U1 layer.
On the obtained U1 layer, a coating solution M0 for a layer not containing metal particles is applied using a wire bar so that the average thickness after drying is 20 nm, heated at 130 ° C. for 1 minute, and dried. Solidified.
Using the wire bar, the coating solution D10 is applied to the opposite side of the surface of the coating film on which M0 is applied so that the coating amount of the dye D-10 is 60 mg / m ^2. It was applied, heated at 130 ° C. for 1 minute, dried and solidified to form a D10 layer.
Thus, the coating film 4 for the infrared shielding film of Comparative Example 3 was produced.

[Example 2]
-Production of coating film 5-
A coating film 5 for an infrared shielding film of Example 2 was produced in the same manner as in Comparative Example 3 except that the coating liquid M0 was changed to the coating liquid M1.

[Comparative Example 4]
-Preparation of aqueous dye dispersion BD-28-
A dye aqueous dispersion BD-28 was prepared in the same manner as the dye aqueous dispersion BD-10, except that the pyrrolopyrrole dye (D-10) was changed to a pyrrolopyrrole dye (D-28) having the structure shown below. . The obtained fine particles were observed with an electron microscope and found to be irregular fine particles having an average particle diameter of 60 nm.

-Preparation of coating liquid D28 for pigment dispersion-containing layer D28-
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration 30% by mass) 1.83 parts by mass Binder polymer: Pluscoat Z-592
(Solid Chemical Industries, Ltd., solid content 25%) 3.3 parts by mass Surfactant B: Aronactee CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.18 parts by mass Dye aqueous dispersion BD-28 25.0 parts by mass Water 39.63 parts by mass IPA 25.94 parts by mass

-Creation of coating film 6-
A coating film 6 for an infrared shielding film of Comparative Example 4 was produced in the same manner as Comparative Example 2 except that the coating liquid D10 was changed to the coating liquid D28.

[Example 3]
-Creation of coating film 7-
A coating film 7 for an infrared shielding film of Example 3 was produced in the same manner as in Example 1 except that the coating liquid D10 was changed to the coating liquid D28.

[Comparative Example 5]
-Creation of coating film 8-
A coating film 8 for an infrared shielding film of Comparative Example 5 was produced in the same manner as Comparative Example 3 except that the coating liquid D10 was changed to the coating liquid D28.

[Example 4]
-Creation of coating film 9-
A coating film 9 for an infrared shielding film of Example 4 was produced in the same manner as in Example 2 except that the coating liquid D10 was changed to the coating liquid D28.

[Comparative Example 6]
A coating solution DI-2 having the following composition was prepared using a heptamethine dye (I-2) having the structure shown below.
-Preparation of coating liquid DI-2 for dye dispersion containing layer DI-2-
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration 30% by mass) 1.83 parts by mass Binder polymer: Pluscoat Z-592
(Solid Chemical Industries, Ltd., solid content 25%) 3.3 parts by mass Surfactant B: Aronactee CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content 1% by mass) 1.18 parts by mass Heptamethine dye (I-2) 0.42 parts by mass Water 66.64 parts by mass IPA 25.94 parts by mass

-Creation of coating film 10-
On the surface of a PET film (A4300, manufactured by Toyobo Co., Ltd., thickness: 75 μm), the coating liquid DI-2 for the pigment dispersion-containing layer was applied using a wire bar, and the coating amount of the pigment I-2 was 30 mg / m. ² was applied. Thereafter, the mixture was heated at 130 ° C. for 1 minute, dried and solidified to form a DI-2 layer.
Further, on the DI-2 layer, a coating solution M0 for a layer not containing metal particles was applied using a wire bar so that the average thickness after drying was 20 nm.
Then, it heated at 130 degreeC for 1 minute, dried and solidified, and produced the coating film 10 for infrared shielding films of the comparative example 6.

[Example 5]
-Creation of coating film 11-
A coating film 11 for an infrared shielding film of Example 5 was prepared in the same manner as in Comparative Example 6 except that the coating liquid M0 was changed to the coating liquid M1.

[Comparative Example 7]
-Creation of coating film 12-
In the same manner as in Comparative Example 3, except that the coating liquid D10 was changed to the coating liquid DI-2 and the coating amount of the dye I-2 was changed to 30 mg / m ² , the coating film 12 for the infrared shielding film of Comparative Example 7 was formed. Produced.

[Example 6]
-Creation of coating film 13-
A coating film 13 for an infrared shielding film of Example 6 was produced in the same manner as in Comparative Example 7 except that the coating liquid M0 was changed to the coating liquid M1.

[Comparative Example 8]
A coating solution DM0 having the following composition was prepared.
-Preparation of DM0 layer coating solution DM0 containing infrared dye-
Polyurethane aqueous solution: Hydran HW-350
(DIC Co., Ltd., solid content concentration: 30% by mass) 0.27 parts by mass Surfactant A: F Ripar 8780P
(Made by Lion Co., Ltd., solid content 1% by mass) 0.96 parts by mass Surfactant B: Aronactee CL-95
(Manufactured by Sanyo Chemical Industries, Ltd., solid content: 1% by mass) 1.19 parts by mass 1% inert aqueous gelatin solution 32.74 parts by mass 1- (5-methylureidophenyl) -5-mercaptotetrazole (Wako Pure Chemical ( Co., Ltd., solid content 2% by mass) 0.61 parts by mass Heptamethine dye (I-2) 0.66 parts by mass Water 33.57 parts by mass Methanol 30.00 parts by mass

-Creation of coating film 14-
On the surface of a PET film (A4300, manufactured by Toyobo Co., Ltd., thickness: 75 μm), the coating liquid U1 for the coating layer U1 is used as a U1 layer so that the average thickness after drying becomes 100 nm using a wire bar. Applied. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and formed U1 layer.
Furthermore, the coating liquid M1 for metal particle content layers was apply | coated on the U1 layer so that the average thickness after drying might be set to 50 nm using the wire bar. Then, it heated at 130 degreeC for 1 minute, dried and solidified, and produced the coating film 14 for the infrared shielding film of the comparative example 8 (preparation of the coating film 14).

[Example 15]
-Preparation of DM1 layer coating solution DM1 containing infrared dye-
A coating solution DM1 was prepared in the same manner as the coating solution DM0 except that the 1% gelatin inert aqueous solution was changed to the silver tabular grain dispersion B1.

-Creation of coating film 15-
A coating film 15 for an infrared shielding film of Example 7 was prepared in the same manner as in Comparative Example 8 except that the coating liquid DM0 was changed to the coating liquid DM1.

-Creation of coating film 16-
A coating film 16 for a Blank film was prepared in the same manner as in Comparative Example 1 except that the coating liquid M1 was changed to the coating liquid M0.

[Evaluation]
-Optical performance evaluation-
(Formation of adhesive layer)
The adhesive layer was laminated | stacked with respect to the surface of the metal particle content layer of each produced coating film. As the pressure-sensitive adhesive layer (pressure-sensitive adhesive), PET-W manufactured by Sanritz Co., Ltd. was used, and the surface of the PET-W from which one release sheet was peeled was bonded to the surface of the metal particle-containing layer of the infrared shielding film. . The obtained laminates were used as the infrared shielding films of Examples 1-7, the infrared shielding films of Comparative Examples 1-8, and the Blank film.

(Measurement of reflection and transmission spectra for evaluation of heat ray reflectance and heat ray transmittance by pigment and silver tabular grains)
The adhesive layer of the infrared shielding film of each Example and the comparative example was affixed on the blue plate glass of thickness 3mm. The reflection spectrum and transmission spectrum of the bonded structure thus obtained were measured using an ultraviolet-visible near-infrared spectrometer (manufactured by JASCO Corporation, V-670). An integrating sphere unit (INS-723, manufactured by JASCO Corporation) was used for reflection spectrum and transmission spectrum measurement.
FIG. 8 shows the reflection spectrum and the transmission spectrum of Comparative Examples 1 and 6, Example 5 and the Blunk film using the

coating films

1, 10, 11, and 16, respectively.
Moreover, the difference with respect to the Blunk film of the reflection spectrum obtained with respect to each sample was calculated | required in 700 nm to 1700 nm, and the average value (%) was described in following Table 1 as an average heat ray reflectance of each sample.

(Evaluation of storage stability)
Further, a laminated structure in which the adhesive layer of the infrared shielding film of each example and comparative example was stretched on glass was subjected to the conditions of Xenon lamp strength 120 W / m ² (300 to 400 nm), relative humidity 40%, and 55 ° C. Continuous light irradiation was performed for 10 days, and then the spectrum of the sample was measured by the same method as the optical performance evaluation described above. The increase rate (%) of the transmittance after light irradiation with respect to the transmittance before light irradiation at the peak wavelength of the dye was determined according to the following formula and evaluated as storability.
100% × {(transmittance after light irradiation) − (transmittance before light irradiation) / (transmittance before light irradiation)}
The results are shown in Table 1 below.

Table 1 shows the total film thickness of the coated material excluding the support.

As shown in Table 1 above, in each example, by using silver tabular grains and a dye in combination, in the case of Comparative Example 1 in which the silver tabular grain-containing layer alone has silver tabular grains, or in Comparative Examples 2 to 8 of the dye alone. Compared with the case, the reflectance of the heat ray could be increased. In addition, it was found that a reflectance greater than the sum of the reflectances of the silver tabular grains or the pigment alone can be realized (for example, from the sum of the average heat ray reflectances of 700 to 1700 nm of the infrared shielding films of Comparative Example 1 and Comparative Example 2). In addition, the average heat ray reflectance of 700 to 1700 nm of the infrared shielding film of Example 1 is higher). As shown in FIG. 8, the reflection increases even in a wavelength region where the reflection alone does not occur. This unexpected effect is called reflection superaddition.

Further, in Table 1 above, the comparison between Examples 1, 3 and 5 shows that when the I-2 dye is used, the heat ray reflectance is higher than when the D-10 or D-28 dye is used. Was found to be preferable.
In particular, it was found from the comparison between Examples 5 to 7 that the reflectance was high when the dye was introduced into the silver tabular grain-containing layer.
In addition, the storage stability largely depends on the dye, but in any dye, Example 2 in which the dye was introduced into the backcoat layer on the lower layer side (opposite side of the support) of the silver tabular grain-containing layer with respect to incident light. In the case of 4 and 6, superaddition is not observed, but in the case of Examples 1, 3 and 5 in which a dye is introduced into the undercoat layer on the lower layer side of the silver-containing layer or the silver tabular grain-containing layer It was found to be good.

In any of the examples, the total thickness of all the coating layers (referred to as the total film thickness) is 0.4 μm or less, which is significantly thinner than the example described in Patent Document 1, High trackability and many uses.

[Examples 11 and 12]
In the coating films 3 and 5 prepared in Examples 1 and 2, the ITO hard coat coating solution (EI-1 manufactured by Mitsubishi Materials Corporation) was dried on the surface opposite to the coated surface of the silver tabular grain dispersion of the PET film. The wire coating bar no. 10 (RDS Webster NY Co., Ltd.) was applied to provide a metal oxide particle-containing layer as a backcoat layer. An adhesive layer was provided on the metal particle-containing layer in the same manner as in Examples 1 and 2 except that the obtained coating film was used, and infrared shielding films of Examples 11 and 12 were produced.
In addition, it turned out that content in the said metal oxide particle content layer of the said ITO particle | grains measured as follows is 3.0 g / m < ² >.

-Measurement of ITO particle content-
The content of the ITO particles with respect to the mass of the entire infrared shielding film is obtained by eluting the ITO particles in a fixed area of the entire heat ray shielding infrared shielding film into methanol, measuring the mass of the ITO particles by fluorescent X-ray measurement, Calculated by dividing by a constant area.

[Example 22]
-Preparation of coating solution UV1 for UV absorbing layer-
A coating solution UV1 for an ultraviolet absorbing layer having the composition shown below was prepared.
Composition of coating solution UV1 for ultraviolet absorbing layer:
Ultraviolet absorber: Tinuvin 326 10 parts by mass (Ciba Japan)
Binder: 10 mass% polyvinyl alcohol solution 10 mass parts Water 30 mass parts These were mixed and the volume average particle diameter was adjusted to 0.6 micrometer using the ball mill.

-Formation of UV absorbing layer-
In the coating film 5 created in Example 2, on the metal particle-containing layer of the infrared shielding film, the coating solution UV1 for the ultraviolet absorbing layer is dried to an average thickness of 0.5 μm using a wire bar. It was applied as follows. Then, it heated at 100 degreeC for 2 minute (s), dried and solidified, and formed the ultraviolet absorption layer which serves as an overcoat layer.
Thereafter, in the same manner as in Example 12, a metal oxide particle-containing layer was provided as a backcoat layer on the back side of the PET film on which the silver tabular particle dispersion was applied, and the metal oxide particle-containing layer / PET film. The laminated body laminated in the order of / undercoat layer U1 / metal particle containing layer containing tabular grains / ultraviolet absorbing layer serving as an overcoat layer was used as an infrared shielding film.

-Formation of adhesive layer-
After washing the surface of the obtained infrared shielding film, the adhesive layer was bonded together. As a pressure-sensitive adhesive layer (pressure-sensitive adhesive), PET-W manufactured by Sanritz Co., Ltd. was used, and the surface of one of the PET-W peeled sheets was bonded to the surface of the ultraviolet ray absorbing layer of the infrared shielding film. By the above, the infrared shielding of Example 22 laminated | stacked in order of the metal oxide particle content layer / PET film / undercoat layer U1 / the metal particle content layer containing a tabular grain / the ultraviolet absorption layer serving also as the overcoat layer / the adhesive layer. A film was prepared.

The optical performance of the infrared shielding films of Examples 11, 12, and 22 was evaluated in the same manner as in Examples 1 and 2. As a result, the effect of increasing the heat ray reflectance was confirmed by the combined use of the pigment and the silver tabular grains.

Since the infrared shielding film of the present invention has a high heat ray reflectivity and excellent heat shielding performance, for example, as a film for automobiles, buses, etc., a laminated structure, a film for building materials, a laminated structure, etc. It can be suitably used as various members that are required to prevent this.

DESCRIPTION OF SYMBOLS 1 Polymer film which is a base material 2 Metal particle content layer 3 Metal flat particle 4 Overcoat layer (it is preferable that an ultraviolet absorber is included)
5 Undercoat layer 10 Infrared shielding film 11 Adhesive layer 12 Backcoat layer 13 Metal oxide particles 14 Metal oxide particle layer D Diameter L Thickness F (λ) Particle existing region thickness E5-T Infrared shielding film of Example 5 Transmission spectrum E5-R Reflection spectrum of the infrared shielding film of Example 5 C1-T Transmission spectrum of the infrared shielding film of Comparative Example 1 C1-R Reflection spectrum of the infrared shielding film of Comparative Example 1 C6-T Infrared shielding of Comparative Example 6 Transmission spectrum of film C6-R Reflection spectrum of infrared shielding film of Comparative Example 6 Transmission spectrum of BT Blunk film Reflection spectrum of BR Blunk film

Claims

An infrared shielding film having a metal particle-containing layer containing metal particles and containing a compound having absorption in the infrared region.
The infrared shielding film according to claim 1, wherein the metal particles have 60% by number or more of flat metal particles.
3. The infrared shielding film according to claim 1, wherein at least one layer has a transmission spectrum peak in a region of 800 to 2000 nm.
The compound having absorption in the infrared region is a compound represented by the following general formula (1) or a compound represented by the following general formula (2). The infrared shielding film as described in the item.

(In the general formula (1), Z 1 and Z 2 are each independently a non-metallic atom group that forms a 5- or 6-membered nitrogen-containing heterocycle. R 1 and R 2 are each independently a fatty group. L 1 is a methine chain composed of 3 methines. A and b are each independently 0 or 1.)

(In General Formula (2), R 1a and R 1b may be the same or different and each independently represents an alkyl group, an aryl group or a heteroaryl group. R 2 and R 3 each independently represent a hydrogen atom. Or at least one is an electron-withdrawing group, and R 2 and R 3 may combine to form a ring, and R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted group Represents a boron or metal atom, and may be a covalent bond or a coordinate bond with at least one group of R 1a , R 1b and R 3. )
The infrared shielding film according to claim 4, wherein the compound having absorption in the infrared region is a compound represented by the general formula (2).
6. The layer containing a compound having absorption in the infrared region contains 20 to 190 mg / m 2 of a compound having absorption in the infrared region. Infrared shielding film.
The infrared shielding film according to any one of claims 1 to 6, wherein the metal particles contain at least silver.
The infrared shielding film according to any one of claims 1 to 7, wherein the metal particles have 60% by number or more of hexagonal or circular silver tabular grains.
The infrared shielding film according to any one of claims 1 to 8, wherein the metal particles are silver tabular grains having an average grain thickness of 20 nm or less.
The infrared shielding film according to any one of claims 1 to 9, wherein the metal particles are silver tabular grains having an aspect ratio (average particle diameter / average particle thickness) of 3 to 100.
The infrared shielding film according to any one of claims 1 to 10, which has a transmission peak between 800 nm and a reflection peak of the metal particle in a transmission spectrum.
The infrared shielding film according to any one of claims 1 to 11, further comprising an ultraviolet absorber.
The infrared ray shielding film according to claim 12, further comprising an adhesive layer, wherein the ultraviolet absorber is contained in the adhesive layer or a layer between the adhesive layer and the metal particle-containing layer.
The infrared shielding film according to any one of claims 1 to 13, further comprising a support.
The infrared shielding film according to claim 14, comprising a dye-containing layer containing a compound having absorption in the infrared region on the same side of the support as the metal particle-containing layer.
The infrared shielding film according to claim 14 or 15, further comprising an undercoat layer between the support and the metal particle-containing layer.
The infrared shielding film according to any one of claims 14 to 16, further comprising a backcoat layer on a surface of the support opposite to the metal particle-containing layer.
The infrared shielding film according to claim 17, wherein the compound having absorption in the infrared region is contained in at least one of the metal particle-containing layer, the undercoat layer, and the backcoat layer.